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191.
Mousumi Sannigrahi Patrick Pinto T.M. Chan Neng-Yang Shih F. George Njoroge 《Tetrahedron letters》2006,47(28):4877-4880
An efficient and practical synthesis of sterically hindered N-substituted lactams has been developed starting from simple starting materials. The stereochemistry of the synthetically useful N,N acetal intermediate has been established. 相似文献
192.
Two new types of iso-oxacephems have been synthesized in which a phosphonate group replaces either the carboxyl group or C(3). The latter compound exists as a stable trialkoxyphosphonium ylide. Potassium thioacetate and O2 in DMF are transformed in an autocatalytic, probably sulfur-catalyzed process to CH3COOK and sulfur; the latter two reagents are sufficient to transform the methanesulfonate 7 to the isopenam 15 . 相似文献
193.
A quantitative compressed pellet infrared method used together with a micro-distillation to effect separation of the isomer has been developed and reported here for the analysis of ortho-, meta-, and para-terphonyl. The terphenyl content is determined on fractions isolated by distillation from radiation damaged samples. The compressed pellet infrared method is preferred instead of the more conventional solution technique since smaller quantities of isolated terphcnyl are required. The pellet method is applicable also to polyphenyls higher than the terphenyls. The solution technique is not due to the insolubility of the polyphenyls. It is expected that the compressed pellet spectral method developed here might well find application in the analysis of compounds other than polyphenyls. Results presented here appear to be the, first quantitative infrared data reported in the literaturu on polyphenyl compounds. 相似文献
194.
Bashiardes G Chaussebourg V Laverdan G Pornet J 《Chemical communications (Cambridge, England)》2004,(1):122-123
A new synthesis of benzo[1,2]oxasiloles is described, wherein an unprecedented intramolecular allylic transposition takes place probably involving a pentavalent silicon intermediate. 相似文献
195.
George Holinga 《Tetrahedron letters》2005,46(47):8245-8247
Dibromocarbene reacts with tertiary-butylisocyanide to form a ketenimine. The absolute rate constant of the reaction (kTBI = 2.3 × 109 M−1 s−1) was determined by laser flash photolysis techniques with UV-vis detection of the dibromocarbene-pyridine ylide. The ketenimine was detected by TRIR spectroscopy at 2040 cm−1. Isocyanide trapping of carbenes to form ketenimines is proposed as a general method of studying IR silent carbenes by TRIR spectroscopy. 相似文献
196.
Phenol is quantified rapidly and accurately by the 4-aminoantipyrine spectrophotometric method after adding 15 g of sodium chloride to a 25-ml sample and distilling in a Semimicro steam distillation apparatus of the Pregl—Parnas—Wagner type. The large amount of sodium chloride provides a saturated solution of the salt during the course of the distillation and causes most of the phenol to be contained in the first few milliliters of distillate. The method has been used to quantify up to 25 mg of phenol per 25 ml. 相似文献
197.
Volumetric heat capacities of the six binary mixtures formed from cyclopentane, cyclohexane, cycloheptane and cyclooctane were determined at 298.15 K in a Picker flow microcalorimeter. Excess heat capacities obtained from the results are compred with the temperature variation of excess enthalpies from the literature. 相似文献
198.
VOF3 is soluble in acetonitrile but is slowly reduced to give a vanadyl (IV) species as one product. It reacts rapidly with Me3SiNet2 in MeCN below ambient temperature; fluorine is replaced by -NEt2 ligands but the spectroscopic and magnetic properties of the products indicate that, in addition, reduction to VIV occurs not some extent. The products are formulated as VOF3-n(NEt2)n containing small quantities of VOF2-m(NEt2)m(NEt2H) (n = 1-3, m = 0-2). A similar reaction occurs between VOF3 and Me3SiOMe but with Me3SiOSiMe3 only VO2F is formed. 相似文献
199.
Kai-Shue Lam I. Harold Zimmerman Jian-Min Yuan John R. Laing Thomas F. George 《Chemical physics》1977,26(3):455-486
Collion-induced emission in molecular systems in an intense laser field is studied using the semiclassical approach, with a view towards cooperative chemical and optical pumping in laser production. The formalism is developed with the electronic-field representation, which treats collision and radiative interaction on the same footing. Electronic-field surfaces can be regarded as forming spectra for spontaneous emission; and particular emission events can be accounted for by propagating classical trajectories on emission electronic-field surfaces. Pre-emission loss from the excited state is dealt with by propagating classical trajectories on a loss surface along a complex contour of emission branch points. This loss surface is derived on the basis of localized radiative couplings between electronic-field states and provides a framework to treat the general problem of discrete state-continuum interactions. The formalism is applied to a two-state, collinear exponential model to compute S-matrix elements and transition probabilities between asymptotic states. 相似文献
200.
Reza Dabesrani Robert H. Sik Donald G. Davis George Dubay Colin F. Chignell 《Photochemistry and photobiology》1993,58(3):367-373
Abstract— The photochemistry, photophysics, and photosensitization (Type I and II) of indomethacin (IN) (N-[p-chlorobenzoyl]-5-methoxy-2-methylindole-3-acetic acid) has been studied in a variety of solvents using NMR, high performance liquid chromatography-mass spectroscopy, transient spectroscopy, electron paramagnetic resonance in conjunction with the spin trapping technique, and the direct detection of singlet molecular oxygen (l O2) luminescence. Photodecomposition of IN (λex > 330 nm) in degassed or air-saturated benzene proceeds rapidly to yield a major (2; N-[p-chlorobenzoyl]-5-methoxy-2-methyl-3-methylene-indoline) and a minor (3; N-[p-chlorobenzoyl]-5-methoxy-2, 3-dimethyl-indole) decarboxylated product and a minor indoline (5; 1-en-5-methoxy-2-methyl-3-methylene-in-doline), which is formed by loss of the p-chlorobenzoyl moiety. In air-saturated solvents two minor oxidized products 4 (N-[p-chlorobenzoyl]-5-methoxy-2-methylindol-3-aldehyde) and 6 (5-methoxy-2-methyl-indole-3-aldehyde) are also formed. When photolysis was carried out in 18O2-saturated benzene, the oxidized products 4 and 6 contained 18O, indicating that oxidation was mediated by dissolved oxygen in the solvent. In more polar solvents such as acetonitrile or ethanol, photodecomposition is extremely slow and inefficient. Phosphorescence of IN at 77 K shows strong solvent dependence and its emission is greatly reduced as polarity of solvent is increased. Flash excitation of IN in degassed ethanol or acetonitrile produces no transients. A weak transient is observed at 375 nm in degassed benzene, which is not quenched by oxygen. Irradiation of IN (λex > 325 nm) in N2-gassed C6H6 in the presence of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) results in the trapping of two carbon-centered radicals by DMPO. One adduct was identified as DMPO/.COC6H4-p-CI, while the other was probably derived from a radical formed during IN decarboxylation. In air-saturated benzene, (hydro) peroxyl and alkoxyl radical adducts of DMPO are observed. A very weak luminescence signal from 1O2 at 1268 nm is observed initially upon irradiation (λex= 325 nm) of IN in air-saturated benzene or chloroform. The intensity of this 1O2 signal increases as irradiation is continued suggesting that the enhancement in 1O2 yield is due to photoproduct(s). Accordingly, when 2 and 3 were tested directly, 2 was found to be a much better sensitizer of 1O2 than IN. In air-saturated ethanol or acetonitrile no IN 1O2 luminescence is detected even on continuous irradiation. The inability of IN to cause phototoxicity may be related to its photo stability in polar solvents, coupled with the low yield of active oxygen species (1O2, O2?-) upon UV irradiation. 相似文献